CN110106430A - The method for preparing alnico using waste nickel hydrogen battery recycling - Google Patents
The method for preparing alnico using waste nickel hydrogen battery recycling Download PDFInfo
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- CN110106430A CN110106430A CN201910341608.3A CN201910341608A CN110106430A CN 110106430 A CN110106430 A CN 110106430A CN 201910341608 A CN201910341608 A CN 201910341608A CN 110106430 A CN110106430 A CN 110106430A
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- alnico
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
- C22C38/105—Ferrous alloys, e.g. steel alloys containing cobalt containing Co and Ni
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The present invention provides a kind of methods for preparing alnico using waste nickel hydrogen battery recycling, waste nickel hydrogen battery is crushed and sorts to obtain positive and negative anodes active material powder, diaphragm, nickel material and iron material, iron material is placed in the coreless induction furnace that temperature is 1300~1550 DEG C and carries out melting and stirs, electrode carbon reaction between carbon and oxygen is added in coreless induction furnace later and obtains alloy intermediate, then it is 1400~1650 DEG C that ferrous sulfide is added in the alloy intermediate in coreless induction furnace and controls high frequency furnace temperature, alloy semi-finished product are made after stirring fishing slag, the mass content of each metallic element and the deviation for preparing the mass content of each metallic element needed for alnico in foundation alloy semi-finished product, corresponding pure metal is filled into alloy semi-finished product, pure metal stirs evenly after being completely melt in coreless induction furnace, later Casting, which forms casting, by casting through sand removal --- obtains alnico after annealing --- magnetic-field heat treatment --- mill processing.The method of the present invention, simple process, novelty, recovery value are higher.
Description
Technical field
The present invention relates to a kind of methods for preparing alnico using waste nickel hydrogen battery recycling.
Background technique
With the fast development of China's new-energy automobile industry, the recycling of retired power battery will become important emerging neck
Domain, upstream materials demand sharp rise, and cause countries in the world and grab the raw material such as nickel, cobalt.Nickel-metal hydride battery is as mixed motor-car
The amount of core drive, old and useless battery increases year by year, and nickel, the iron content in waste nickel hydrogen battery are all higher.Traditional nickel
Hydrogen battery recovery method generally passes through wet-leaching --- sodium sulphate sink rare earth --- and removes when pretreatment obtains iron material
The processes such as iron --- extraction --- crystallization are recycled, long flow path, and investment is larger, and added value of product is low.
Summary of the invention
The present invention is intended to provide a kind of simple process, novelty, recovery value are higher to utilize waste nickel hydrogen battery recycling system
The method of standby alnico.
The present invention is realized by the following scheme:
A method of alnico being prepared using waste nickel hydrogen battery recycling, is carried out according to the following steps,
(a) waste nickel hydrogen battery is crushed and sorts to obtain positive and negative anodes active material powder, diaphragm, nickel material and iron material
Material；Broken includes rough and torn, two steps of thin broken, and when broken material sorts, the thinner positive and negative anodes active material powder of particle is first
It is sized out, later surplus material is passed through to gravity separation again and go out diaphragm, finally by surplus material by changing magnetic field strength
Mode, sub-elect nickel material and iron material；In the iron material, weight of iron content be 60~83%, nickel mass content be 5~
15%, cobalt mass content is 0.1~10%, and rare earth mass content is 1~5%；
(b) iron material that sorting obtains in step (a) is placed in the coreless induction furnace that temperature is 1300~1550 DEG C and is melted
It refines and stirs evenly, electrode carbon reaction between carbon and oxygen certain time is added in coreless induction furnace later and obtains alloy intermediate；General iron material
Material 30~60min of melting in coreless induction furnace can be completely melt；
(c) it is 1400~1650 that ferrous sulfide is added in the alloy intermediate in coreless induction furnace and controls high frequency furnace temperature
DEG C, alloy semi-finished product are made in stirring fishing slag after a certain period of time；In actual production process, the temperature of coreless induction furnace not will do it drop generally
Temperature adjustment, that is to say, that if the temperature control of coreless induction furnace in step (b) is 1450 DEG C, then the coreless induction furnace in step (c)
Temperature remains 1450 DEG C or up adjusts；
(d) according to the mass content of each metallic element in alloy semi-finished product made from step (c) and Al-Ni-Co permanent magnet is prepared
The deviation of the mass content of each metallic element needed for alloy fills into corresponding pure metal in Xiang Hejin semi-finished product, and pure metal is in height
It is stirred evenly after being completely melt in frequency furnace, casting forms casting later, --- annealing --- the magnetic field Re Chu by casting through sand removal
Reason --- alnico is obtained after mill processing.Alnico there are many specification multiple standards, needed for gold
The mass content for belonging to element is also different, and in specific preparation, the dosage of the pure metal filled into can be according to aluminium nickel in each standard
The mass content of required each metallic element of Co permanent magnetic alloy is specifically calculated.For example, nickel metal in alloy semi-finished product
The mass content of element is lower than the mass content for preparing nickel metallic element needed for alnico, then fills into pure iron metal.
In view of burn-off rate, the corresponding pure metal filled into is fritter or powdered.
Further, in the step (b), the addition quality of electrode carbon is the 15~20% of iron material quality, and carbon oxygen is anti-
The time control answered is 30~60min.Carbon content in electrode carbon is generally >=99.9%.
Further, in the step (c), the addition quality of ferrous sulfide is 3~5% of weight among alloy, is stirred
The time control for mixing fishing slag is 30~45min.Under normal circumstances, the ferrous sulfide is to analyze pure, principal component FeS content >
80%.
Further, in the step (d), the temperature control of coreless induction furnace is 1600~1650 DEG C, and the temperature of casting is than high
The temperature of frequency furnace is 50 DEG C high.Sand removal, annealing in step (d), magnetic-field heat treatment, mill are processed as preparing alnico
Common process.
The method for preparing alnico using waste nickel hydrogen battery recycling of the invention, simple process, novelty are raw
It is fast to produce efficiency, recycling alloy product purity is high can be used for the fields such as instrument and meter, motor, electro-acoustic element, magnetic machinery.This hair
The bright method for preparing alnico using waste nickel hydrogen battery recycling, highly-safe, pollution is small, is suitable for extensive
Processing recycling waste nickel hydrogen battery.
Specific embodiment
The invention will be further described with reference to embodiments, but the invention is not limited to the statements of embodiment.
Embodiment 1
A method of alnico being prepared using waste nickel hydrogen battery recycling, is carried out according to the following steps,
(a) waste nickel hydrogen battery is crushed and sorts to obtain positive and negative anodes active material powder, diaphragm, nickel material and iron material
Material；Broken includes rough and torn, two steps of thin broken, and when broken material sorts, the thinner positive and negative anodes active material powder of particle is first
It is sized out, later surplus material is passed through to gravity separation again and go out diaphragm, finally by surplus material by changing magnetic field strength
Mode, sub-elect nickel material and iron material；Through detecting, in iron material, weight of iron content is 80%, and nickel mass content is 8%,
Cobalt mass content is 8%, and rare earth mass content is 3%；
(b) iron material that sorting obtains in step (a) is placed in the coreless induction furnace that temperature is 1550 DEG C and carries out melting 30min
And stir evenly, the 20% electrode carbon reaction between carbon and oxygen 40min that iron material quality is added in coreless induction furnace later is obtained in alloy
Mesosome, wherein carbon content >=99.9% in electrode carbon；
(c) the pure ferrous sulfide of 5% analysis of weight among alloy is added simultaneously in the alloy intermediate in coreless induction furnace
Controlling high frequency furnace temperature is 1600 DEG C, the principal component FeS content > 80% of ferrous sulfide, and alloy is made after stirring fishing slag 45min
Semi-finished product；Each metallic element mass content of alloy semi-finished product is detected, specific data are shown in Table 1:
The mass content of 1 each metallic element of alloy semi-finished product of table
| Element term | Fe | Ni | Co |
| Mass content (%) | 75.17 | 12.63 | 11.43 |
(d) according to the mass content of each metallic element in alloy semi-finished product made from step (c) and preparation GB4753-1984
LNG16 standard alnico needed for each metallic element mass content deviation, mend in Xiang Hejin semi-finished product
Enter corresponding pure metal fritter i.e. fine aluminium, pure nickel, pure cobalt, pure titanium, fine copper slug, pure metal fritter is 1600 DEG C in temperature
Stirred evenly after being completely melt in coreless induction furnace, casting forms casting at 1650 DEG C later, by casting through sand removal --- it moves back
Alnico is obtained after the processing of fiery --- magnetic-field heat treatment --- mill.
The alnico that embodiment 1 is prepared carries out component content detection, and specific data are shown in Table 2, from table 2
Middle data can be seen that the alnico that embodiment 1 is prepared meets the LNG16 standard of GB4753-1984.
The component content for the alnico that 2 embodiment 1 of table is prepared
| Element term | Al | Ni | Co | Ti | Cu | Fe |
| Mass fraction (%) | 9.56 | 20.0 | 14.9 | 0.5 | 4.1 | Surplus |
Embodiment 2
A method of alnico, the benefit of step and embodiment 1 are prepared using waste nickel hydrogen battery recycling
The step of preparing the method for alnico with waste nickel hydrogen battery recycling is essentially identical, the difference is that:
1, in step (a), through detecting, in iron material, weight of iron content is 80%, and nickel mass content is 15%, cobalt quality
Content is 0.1%, and rare earth mass content is 5%；
2, in step (b), the temperature control of coreless induction furnace is 1300 DEG C, and smelting time control is 60min；The addition of electrode carbon
Quality is the 15% of iron material quality, and the control of reaction between carbon and oxygen time is 60min；
3, in step (c), the temperature control of coreless induction furnace is 1400 DEG C, and the addition quality of ferrous sulfide is constitution among alloy
The 3% of amount, stirring fishing slag time control is 30min, detects each metallic element mass content of alloy semi-finished product, specific data are shown in
Table 3:
The mass content of 3 each metallic element of alloy semi-finished product of table
| Element term | Fe | Ni |
| Mass content (%) | 75.17 | 20.63 |
4, mass content and preparation in step (d), according to each metallic element in alloy semi-finished product made from step (c)
The deviation of the mass content of each metallic element needed for the alnico of the LN9 standard of GB4753-1984, to alloy half
Corresponding pure metal fritter i.e. fine aluminium, pure nickel, fine copper slug are filled into finished product, the temperature control of coreless induction furnace is 1650 DEG C, is poured
Casting temperature control is 1700 DEG C.
The alnico that embodiment 2 is prepared carries out component content detection, and specific data are shown in Table 4, from table 4
Middle data can be seen that the alnico that embodiment 2 is prepared meets the LN9 standard of GB4753-1984.
The component content for the alnico that 4 embodiment 2 of table is prepared
| Element term | Al | Ni | Co | Cu | Fe |
| Mass fraction (%) | 13 | 24 | 0.1 | 3 | Surplus |
Claims (5)
1. a kind of method for preparing alnico using waste nickel hydrogen battery recycling, it is characterised in that: according to the following steps
It carries out,
(a) waste nickel hydrogen battery is crushed and sorts to obtain positive and negative anodes active material powder, diaphragm, nickel material and iron material；
(b) iron material that sorting obtains in step (a) is placed in the coreless induction furnace that temperature is 1300~1550 DEG C and carries out melting simultaneously
It stirs evenly, electrode carbon reaction between carbon and oxygen certain time is added in coreless induction furnace later and obtains alloy intermediate；
(c) it is 1400~1650 DEG C that ferrous sulfide is added in the alloy intermediate in coreless induction furnace and controls high frequency furnace temperature, is stirred
It mixes fishing slag and alloy semi-finished product is made after a certain period of time；
(d) according to the mass content of each metallic element in alloy semi-finished product made from step (c) and alnico is prepared
The deviation of the mass content of required each metallic element fills into corresponding pure metal in Xiang Hejin semi-finished product, and pure metal is in coreless induction furnace
In be completely melt after stir evenly, later casting form casting, by casting through sand removal --- annealing --- magnetic-field heat treatment ---
Alnico is obtained after mill processing.
2. the method for preparing alnico using waste nickel hydrogen battery recycling as described in claim 1, feature exist
In: in the step (b), the addition quality of electrode carbon is the 15~20% of iron material quality, and the time control of reaction between carbon and oxygen is
30~60min.
3. the method for preparing alnico using waste nickel hydrogen battery recycling as described in claim 1, feature exist
In: in the step (c), the addition quality of ferrous sulfide is 3~5% of weight among alloy, the time control of stirring fishing slag
It is made as 30~45min.
4. the method for preparing alnico using waste nickel hydrogen battery recycling as claimed in claim 3, feature exist
In: the ferrous sulfide is to analyze pure, principal component FeS content > 80%.
5. the method for preparing alnico using waste nickel hydrogen battery recycling as described in Claims 1 to 4 is any,
Be characterized in that: in the step (d), the control of the temperature of coreless induction furnace is 1600~1650 DEG C, the temperature of the temperature of casting than coreless induction furnace
It spends 50 DEG C high.
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| CN201910341608.3A CN110106430B (en) | 2019-04-26 | 2019-04-26 | Method for recycling and preparing alnico permanent magnetic alloy by using waste nickel-hydrogen battery |
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| CN201910341608.3A CN110106430B (en) | 2019-04-26 | 2019-04-26 | Method for recycling and preparing alnico permanent magnetic alloy by using waste nickel-hydrogen battery |
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Cited By (1)
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| CN112458323A (en) * | 2020-10-27 | 2021-03-09 | 先进储能材料国家工程研究中心有限责任公司 | Method for preparing nickel-based alloy by recycling waste nickel-hydrogen battery |
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